EP0564232B1 - Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé - Google Patents
Dérivés du N,N-bis(phosphonométhyl)-2-amino-1-propanol pour inhiber la formation de tartre à pH élevé Download PDFInfo
- Publication number
- EP0564232B1 EP0564232B1 EP93302469A EP93302469A EP0564232B1 EP 0564232 B1 EP0564232 B1 EP 0564232B1 EP 93302469 A EP93302469 A EP 93302469A EP 93302469 A EP93302469 A EP 93302469A EP 0564232 B1 EP0564232 B1 EP 0564232B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- scale
- acid
- ampsa
- phosphonomethyl
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WSQOVFPWCADROX-UHFFFAOYSA-N [1-hydroxypropan-2-yl(phosphonomethyl)amino]methylphosphonic acid Chemical class OCC(C)N(CP(O)(O)=O)CP(O)(O)=O WSQOVFPWCADROX-UHFFFAOYSA-N 0.000 title claims description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 89
- 239000000203 mixture Substances 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 44
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 44
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 230000002401 inhibitory effect Effects 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 14
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical group 0.000 claims description 10
- 229920000570 polyether Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 5
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- ARYGWINSZRGVNG-UHFFFAOYSA-N [1-methoxypropan-2-yl(phosphonomethyl)amino]methylphosphonic acid Chemical compound COCC(C)N(CP(O)(O)=O)CP(O)(O)=O ARYGWINSZRGVNG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 229960003563 calcium carbonate Drugs 0.000 description 34
- 235000010216 calcium carbonate Nutrition 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 229910001868 water Inorganic materials 0.000 description 30
- 150000005215 alkyl ethers Chemical class 0.000 description 26
- 150000001412 amines Chemical class 0.000 description 23
- 230000005764 inhibitory process Effects 0.000 description 22
- -1 anion carbonate Chemical class 0.000 description 18
- 239000003112 inhibitor Substances 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 229910021532 Calcite Inorganic materials 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- 229960005069 calcium Drugs 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000002455 scale inhibitor Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001204 N-oxides Chemical class 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 229920000867 polyelectrolyte Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003352 sequestering agent Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910018828 PO3H2 Inorganic materials 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- NXMXETCTWNXSFG-UHFFFAOYSA-N 1-methoxypropan-2-amine Chemical compound COCC(C)N NXMXETCTWNXSFG-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- GWASTCVCPXFIQT-UHFFFAOYSA-N NC1OP(=O)O1 Chemical class NC1OP(=O)O1 GWASTCVCPXFIQT-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PWOVSTKKOSRWTJ-UHFFFAOYSA-N [2-(2-hydroxyethoxy)ethyl-(phosphonomethyl)amino]methylphosphonic acid Chemical class OCCOCCN(CP(O)(O)=O)CP(O)(O)=O PWOVSTKKOSRWTJ-UHFFFAOYSA-N 0.000 description 1
- YAWYUSRBDMEKHZ-UHFFFAOYSA-N [2-hydroxyethyl(phosphonomethyl)amino]methylphosphonic acid Chemical compound OCCN(CP(O)(O)=O)CP(O)(O)=O YAWYUSRBDMEKHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229960001714 calcium phosphate Drugs 0.000 description 1
- OMAAXMJMHFXYFY-UHFFFAOYSA-L calcium trioxidophosphanium Chemical compound [Ca+2].[O-]P([O-])=O OMAAXMJMHFXYFY-UHFFFAOYSA-L 0.000 description 1
- GVHLBLKTDYODFL-UHFFFAOYSA-N calcium;(2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound [Ca].OCC(P(O)(O)=O)P(O)(O)=O GVHLBLKTDYODFL-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Definitions
- the present invention relates to compositions and methods for inhibiting the formation, deposition and adherence of alkaline earth metal scale deposits, especially calcium carbonate (CaCO 3 ) scale deposits, on metallic surfaces of aqueous systems, especially under conditions of high pH and high calcite concentration, e.g., those found in cycled up cooling tower systems, where those compositions are N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers thereof.
- alkaline earth metal scale deposits especially calcium carbonate (CaCO 3 ) scale deposits
- calcium carbonate scale deposits are incrustation coatings which accumulate on the metallic surfaces of a water-carrying system through a number of different causes.
- Calcium carbonate scale is of particular concern in heat exchange systems employing water, such as, for example, boiler systems, and once-through and open recirculating water cooling systems. Cooling towers are especially significant, particularly where severe conditions, including high pH and high calcite concentrations are encountered.
- the water employed in these systems ordinarily will contain a number of dissolved salts, and the alkaline earth metal cation calcium is usually prevalent, as is the anion carbonate.
- the combination product of calcium cation and carbonate anion will precipitate from the water in which they are carried to form scale deposits when the concentration of the anion and cation comprising the reaction product, i. e., calcium carbonate, exceeds the solubility of the reaction product itself.
- concentrations of calcium ion and carbonate ion exceed the solubility of the calcium carbonate reaction product, a solid phase of calcium carbonate will form as a precipitate. Precipitation of the reaction product will continue until the solubility product concentrations of the constituent ions are no longer exceeded.
- the mechanism of scale formation is apparently one of crystallization of scale-forming salts from a solution which is locally supersaturated in the region adjacent the heating surface of the system.
- the thin viscous film of water in this region tends to become more concentrated than the remainder of the solution outside this region.
- Precipitation is also favored on the heat transfer surface because of the inverse solubility relationship of calcium carbonate.
- the solubility of the scale-forming calcium carbonate salt reaction product is first exceeded in this thin film, and crystallization of calcium carbonate scale results directly on the heating or heat exchange surface.
- alkalinity of the makeup water results in an increasing alkalinity of the water in the overall system, often reaching pH's of 8.5 - 9.5 and even higher.
- Conventional scale inhibiting compositions typically fail in systems having such severe conditions.
- calcium carbonate scale deposits poses a serious problem in a number of regards.
- the calcium carbonate scale which is formed possesses a low degree of heat conductivity.
- a calcium carbonate scale deposit is essentially an insulating layer imposed across the path of heat travel from whatever source to the water of the system.
- the retarded heat transfer causes a loss in cooling efficiency.
- calcium carbonate scale formation facilitates underdeposit corrosive processes, and a substantial calcium carbonate scale deposit will interfere materially with fluid flow. Consequently, calcium carbonate scale is an expensive problem in many industrial water systems, causing delays and shutdowns for cleaning and removal.
- the present invention is directed primarily to preventing or inhibiting the deposition of calcium carbonate scale, the most prevalent type of scale deposit, it is also applicable to inhibiting the deposition of other types of alkaline earth metal scales, especially where those are associated with calcium carbonate scale under the severe conditions described herein.
- alkaline earth metal cations such as calcium and magnesium
- anions such as bicarbonate, carbonate, and phosphate.
- alkaline earth metal scales including but not limited to calcium carbonate, magnesium carbonate, and calcium phosphate. These scales form frequently in the tubes of heat exchangers and on other heat exchange surfaces, such as those in cooling towers. Particular systems or applications areas where severe conditions lead to exceptional buildup of calcium carbonate and related scales, in addition to cycled up cooling towers, include reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
- N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers of the present invention are used in the same range of amounts as threshold inhibitors in the scale inhibition method of the present invention, rather than as sequestering or chelating agents, although the compositions of the present invention have dispersant properties as well and significantly reduce the adherency of any scale deposit which is formed, facilitating its easy removal.
- Scale-forming compounds can be prevented from precipitating by inactivating their cations with chelating or sequestering agents, so that the solubility of their reaction products is not exceeded. Generally, this requires many times as much chelating or sequestering agent as cation, since chelation is a stoichiometric reaction, and these amounts are not always desirable or economical. However, several decades ago, it was discovered that certain inorganic polyphosphates would prevent such precipitation when added in amounts far less than the concentrations needed for sequestering or chelating.
- anionic and cationic polymers can be used as dispersants in accordance with methods known in the art, but the dosage levels necessary to achieve dispersion are in the range of 0.5 - 1.0% by weight of the system being treated, which is many orders of magnitude higher that the dosage levels used for the compositions of the present invention.
- compositions of the present invention are especially useful under severe conditions characterized by a calcite saturation level of 150 X and above, especially 250X and above, and more especially 300X and above, as defined in the paragraph immediately below.
- Another characteristic feature of the severe conditions under which the scale controlling compositions of the present invention are especially useful is high pH, i.e. a pH of 8.5 and higher, particularly a pH of 9 or 10 or even higher.
- a related feature of such severe conditions is high alkalinity.
- Calcium tolerance is a measure of a chemical compound's ability to remain soluble in the presence of calcium ions (Ca 2+ ).
- Ca 2+ calcium ions
- One of the parameters of scale control under severe conditions is pH.
- CaCO 3 threshold inhibitors e.g., 1-hydroxy ethylidene 1,1-diphosphonic acid (HEDP) and amino tri(methylene phosphonic acid) (AMP). These inhibitors precipitate with calcium at alkaline pH's, rendering them useless as threshold scale inhibitors.
- An advantage of the scale inhibiting compositions of the present invention is their ability to maintain a level of resistance to degradation by oxidizing biocides which is sufficient to ensure adequate scale inhibition at dosing levels within the ranges herein described. This is of particular importance in cooling systems such as those using cycled up cooling towers. Such systems maintain a large body of water for a considerable length of time exposed to the atmosphere under conditions which do not include sufficient aeration and exposure to sunlight to provide control of microbial, especially bacterial and fungal, growth. Unchecked, such microorganisms flourish and produce colonies extensive enough to give rise to problems of biofilm blockage of heat exchange surfaces, and clogging of the components of the water transporting apparatus used in operating the cooling system.
- threshold active inhibitor Another type of agent which has been actively explored heretofore as a calcium carbonate scale inhibiting material is the threshold active inhibitor.
- Such materials are effective as scale inhibitors in amounts considerably less than that stoichiometrically required, and this amount, as already mentioned, is termed the threshold amount.
- Inorganic polyphosphates have long been used as such threshold active inhibitors. For examples of such materials, see Fink - US 2,358,222; Hatch - US 2,539,305; and Ralston US 3,434,969.
- Certain water soluble polymers including groups derived from acrylamide and acrylic acid have been used to condition water containing scale-forming calcium carbonate.
- anionic polyelectrolytes such as polyacrylates, polymaleic anhydrides, copolymers of acrylates and sulfonates, and polymers of sulfonated styrenes. See, for example, US 4,640,793; 4,650,591; 4,457,847 ; and 4,671,888.
- large dosages of these polymers are required, which in turn increases operating costs.
- N,N-bis(phosphonomethyl)-2-amino-1-propanol and corresponding lower alkyl ethers of the type which comprise the active ingredient of the compositions of the present invention are known, nor is their use for the control of alkaline earth metal scale, particularly calcium carbonate scale, under severe conditions which include elevated pH and high calcium carbonate saturation levels, with enhanced resistance to degradation by oxidizing biocides. Nevertheless, other phosphonates of related structure are known in the art for scale inhibition use.
- US 4,080,375 discloses methylene phosphonates of amino-terminated oxyalkylates for use as scale inhibitors, but these compositions are not the same as those of the present invention, nor is there any suggestion that such compositions would be useful under severe conditions as defined herein, where phosphonates such as HEDP and AMP give poor results.
- US 4,931,189 discloses aminomethylene phosphonates for inhibiting oil field scale formation involving a high brine environment susceptible to gypsum or barite scale formation. Such use in no way suggests the control of scale under the severe conditions described herein under which the compositions and methods of the present invention operate with surprising success.
- the present invention relates to a compound of the formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl;
- the present invention particularly relates to compounds of the above formulas wherein R is hydrogen, M is hydrogen, and n is 1, giving the compound N,N-bis(phosphonomethyl)-2-amino-1-propanol; and wherein R is methyl, M is hydrogen, and n is 1, giving the compound N,N-bis(phosphonomethyl)-1-methoxy-2-propanamine.
- the present invention further relates to a composition useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds in an aqueous system, comprising N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers therof, of the following formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl.
- the present invention also relates to a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds in an aqueous system
- a composition useful as a deposit control agent to control the formation, deposition and adherence of scale imparting compounds in an aqueous system
- the present invention further relates to a method of inhibiting the formation, deposition and adherence of scale-forming salts in an aqueous system, comprising the step of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives and corresponding lower alkyl ethers.
- the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, and said compound is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L.
- the present invention further relates to a method of inhibiting the formation, deposition and adherence of scale-forming salts in an aqueous system, comprising the step of adding to said system an amount sufficient to establish a concentration of from 1 to 100 mg/L of a composition comprising N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the formula above, together with one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide--methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), ethoxylated methacrylate, itaconic acid (IA), polyether esters of acrylic and methacrylic acids and polyethers based on polyethyleneoxide and polypropyleneoxide and mixtures thereof, especially polyethylene glycol monomethacrylate (PGM), maleic
- the present invention relates to such a method in which calcium carbonate is the scale-forming salt, the aqueous system comprises a cooling tower, said composition is added to the aqueous system being treated in an amount sufficient to establish a concentration of from 10 to 50 mg/L, and said polymer additive is a member selected from the group consisting essentially of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA, 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively), and AA/AMPSA/TBAM.
- the group consisting essentially of 90/10 to 10/90 AA/AMPSA preferably 75/25 and 60/40 AA/AMPSA, 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70
- composition of the present invention useful as a deposit control agent to control the formation, deposition and adherency of scale imparting compounds in an aqueous system comprises N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the formula: where n is an integer of from 1 to 3, inclusive; M is hydrogen or a suitable cation; and R is independently selected from hydrogen and C 1-4 alkyl.
- This key feature of the compounds of the present invention confers significant resistance to degradation by oxidizing biocides, presumably by preventing oxidative attack on the nitrogen atom of the group.
- compositions of the above formula is that wherein M is hydrogen, n is from 1 to 3, more preferably 1, and R is hydrogen, methyl or ethyl, most preferably hydrogen or methyl.
- M is hydrogen
- n is from 1 to 3, more preferably 1
- R is hydrogen, methyl or ethyl, most preferably hydrogen or methyl.
- this group is present initially in the phosphonic acid form or as an alkali metal or other salt of the acid, has no critical bearing on the performance of the overall molecule.
- the compositions of the present invention At the pH's under which the compositions of the present invention function, they are, and must be, in their ionized form.
- M is hydrogen or a suitable cation, and the selection of an appropriate salt form is well within the skill of the art. Alkali metal salts are the most simple, and are preferred for that reason. Overall, however, it is preferred that M is hydrogen.
- the most essential structural feature of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers useful in the compositions and methods of the present invention is the isopropyloxy group, or series of repeating isopropyloxy groups, up to 3 in number, which bridge the diphosphonomethylamino group and the terminal hydrogen (hydroxyl) or lower alkyl ether (lower alkoxyl) group:
- the isopropyloxy group has been found to be unique in providing enhanced scale inhibition activity under the severe conditions defined herein.
- n 1
- the isopropyloxy groups increase in number, there is a gradual decrease in the scale inhibiting efficiency of the overall compound.
- all of these compounds continue to reflect the surprising improvement in performance attributable to the presence of the isopropyloxy group, whether one or more of such groups is present.
- R is preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl, and most preferably methyl.
- the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers of the compositions and methods of the present invention are prepared by phosphonomethylation of the appropriate primary amine which already contains the isopropyloxy moiety or moieties.
- Such primary amine starting materials and their method of preparation are well known.
- the phosphonomethylation of the primary amine is then carried out by a Mannich reaction such as that described in K. Moedritzer and R. Irani, J. Organic Chem. 31(5) 1603-7, "The Direct Synthesis of alpha-Aminomethyl Phosphonic Acids; Mannich-Type Reactions with Orthophosphorous Acid", May 1966.
- the primary amine is added to a mixture of phosphorous acid and water, and concentrated hydrochloric acid is then added slowly, after which the reaction mixture is heated to reflux with addition of aqueous formaldehyde.
- any of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ether compositions of the present invention are used to inhibit the precipitation, deposition, and adherence of scale-forming salts in an aqueous system, they can be effectively employed for that purpose when added in amounts sufficient to establish a concentration in said aqueous system of from 1 to 100 mg/L.
- the amount added will be sufficient to establish a concentration of from 5 to 75 mg/L, and most preferably, the amount added will be sufficient to establish a concentration of from 10 to 50 mg/L of the composition.
- the amounts of that combination which must be added in order to inhibit the formation, deposition and adherence of scale-forming salts in an aqueous system will as a general matter be within the ranges of amounts sufficient to establish the ranges of concentrations of the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers used alone, as recited in detail above. Again, however, calculation of the actual amount is well within the skill of the art.
- inhibitors the precipitation and “inhibiting the formation and deposition” are meant to include threshold inhibition, dispersion, solubilization, or particle size reduction.
- inhibitors the adherence and “increasing the non-adherence”, are meant to define the formation of a scale deposit which is easily removed, e.g., by simple rinsing, i.e., a scale deposit which is not so firmly bonded to the surface to which it is attached that it cannot be removed by simple physical means as opposed to harsh mechanical or chemical treatment.
- scale-forming salts is meant to include any of the scale-forming salts selected from the group consisting essentially of calcium carbonate, calcium phosphate, calcium phosphonate (including calcium hydroxyethylidene diphosphonic acid), and the corresponding magnesium salts.
- aqueous system means commercial or industrial systems utilizing water and involving heat exchange surfaces, usually of metal, including cooling water systems including cooling towers, boiler water systems, desalination systems, gas scrubbers, and thermal conditioning equipment. Of particular importance are those systems which operate under severe conditions as detailed herein, including at least high pH and high calcite concentrations. Typical of such systems are cycled up cooling towers, reverse osmosis systems, sugar refining evaporators, and certain types of gas scrubbers.
- N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether composition of the present invention to an aqueous system will also be straightforward to a person of ordinary skill in this art. It may be added in liquid form by mechanical dispensers of known design. It may also be added in diluted liquid form. The N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether composition may also be combined with other chemical treatment agents for dispensing to the aqueous system; and these in combination may be dispensed in liquid form.
- acrylamide acrylamide
- AA acrylic acid
- AMPSA 2-acrylamide--methyl propane sulfonic acid
- MAA methacrylic acid
- IA itaconic acid
- PGM polyethylene glycol monomethacrylate
- MA maleic anhydride
- MA maleic acid
- TBAM t-butyl acrylamide
- SSS sodium styrene sulfonate
- AHPS 3-allyloxy-2-hydroxy propane sulfonic acid
- vinyl phosphonic acid weight average molecular weight
- compositions include copolymers of 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA.
- Other preferred polymer additives for use with the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivatives, and corresponding lower alkyl ethers and N-oxides of the present invention include 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5, 10 and 20 (having 5, 10 and 20 repeating oxyethylene units, respectively), (having 5 repeating oxyethylene units), and AA/AMPSA/TBAM.
- Combinations using these polymers together with the N,N-bis(phosphonomethyl)-2-amino-1-propanol, derivative, or corresponding lower alkyl ether compositions of the present invention can increase the amount of scale control and deposit control which is achieved under the severe conditions described herein.
- PROCEDURE Scaling water containing 250 mg/L of CO -2 / 3 and 600 mg/L of alkalinity at a pH of 9.0 and 55°C was used to evaluate scale inhibition performance of test solutions over a 24 hr period. Test solutions were analyzed by withdrawing 10 g of test solution and adding it to the appropriate container through a 0.2 ⁇ filter, titrating for calcium, and calculating % inhibition by the Schwarzenbach method.
- the primary amine 1-methoxy-2-propanamine having the structural formula: CH 3 OCH 2 CH(CH 3 )NH 2 (22.28g, 0.25 mole) was added to a mixture of 70% phosphorous acid (58.57g, 0.50 mole), 50 mL of concentrated hydrochloric acid, and deionized water (32.43g) in a 250 mL 3-neck flask fitted with a condenser, a magnetic stirrer, a thermometer and an addition funnel. The reaction mixture was then heated to reflux, and there was then added 81.16g (1.00 mole) of 37% aqueous formaldehyde (HCHO) over a period of about 25 min. The reaction mixture was then refluxed for an additional period of 3 hrs. to complete the reaction. The reaction mixture was then reduced by 20% to yield an aqueous solution of 46.4%. Analysis of the 31 P NMR spectra of this solution indicated the desired product.
- HCHO 37% aqueous formaldehyde
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Claims (12)
- Un composé selon la revendication 1, dans lequel R est l'hydrogène, M est l'hydrogène et n est 1, ce qui donne le composé N,N-bis(phosphonométhyl)-2-amino-1-propanol.
- Un composé selon la revendication 1, dans lequel R est un radical méthyle, M est l'hydrogène et n est 1, ce qui donne le composé N,N-bis(phosphonométhyl)-1-méthoxy-2-propanamine.
- Une composition utile comme agent de régulation de dépôt pour réguler la formation, le dépôt et l'adhésion de composés produisant du tartre dans un système aqueux, comprenant un composé selon l'une quelconque des revendications 1 à 3.
- Un procédé pour inhiber la formation, le dépôt et l'adhésion de sels formant du tartre dans un système aqueux, comprenant l'étape consistant à ajouter audit système une quantité suffisante pour établir une concentration de 1 à 100 mg/l d'une composition selon la revendication 4.
- Un procédé selon la revendication 5, dans lequel le carbonate de calcium est le sel formant du tartre et ladite composition est ajoutée au système aqueux qui est traité selon une quantité suffisante pour établir une concentration de 10 à 50 mg/l.
- Un procédé pour inhiber la formation, le dépôt et l'adhésion de sels formant du tartre dans un système aqueux, comprenant l'étape consistant à ajouter audit système une quantité suffisante pour établir une concentration de 1 à 100 mg/l d'une composition comprenant un composé selon l'une quelconque des revendications 1 à 3, conjointement avec un ou plusieurs éléments choisis parmi le groupe comprenant :les homopolymères, les copolymères et les terpolymères comprenant un ou plusieurs monomères d'acrylamide (AM), d'acide acrylique (AA), d'acide 2-acrylamide-méthyl-propane sulfonique (AMPSA), d'acide méthacrylique (MAA), de méthacrylate éthoxylé, d'acide itaconique (IA), de polyéther-esters d'acide acrylique et d'acide méthacrylique et de polyéthers à base d'oxyde de polyéthylène et d'oxyde de polypropylène et de leurs mélanges, comprenant le monométhacrylate de polyéthylèneglycol (PGM), l'anhydride maléique (MA), l'acide maléique (MA), le t-butyl-acrylamide (TBAM), le styrène-sulfonate de sodium (SSS), le vinyl-sulfonate de sodium, l'acrylate d' hydroxy-propyle, le méthacrylate d' hydroxy-propyle, l'acide 3-allyloxy-2-hydroxy-propane sulfonique (AHPS), et l'acide vinyl-phosphonique, où le poids moléculaire moyen en poids pour de tels additifs polymères se situe dans la gamme d'environ 500 à 250 000.
- Un procédé selon la revendication 7, dans lequel l'additif polymère est choisi parmi le groupe comprenant l'acide polyacrylique et les copolymères 75/25 et 60/40 AA/AMPSA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5 (ayant 5 motifs oxyéthylène se répétant), et AA/AMPSA/TBAM.
- Un procédé selon la revendication 8, dans lequel le carbonate de calcium est le sel formant du tartre et ledit propanol et ledit additif polymère sont ajoutés conjointement au système aqueux qui est traité selon une quantité suffisante pour établir une concentration de 10 à 50 mg/l.
- Un procédé selon la revendication 9, dans lequel le système aqueux qui est traité est un système de refroidissement.
- Une composition utile comme un agent de régulation de dépôt pour réguler la formation, le dépôt et l'adhésion de composés produisant du tartre dans un système aqueux comprenant, en combinaison, un composé selon l'une quelconque des revendications 1 à 3, conjointement avec un ou plusieurs éléments choisis parmi le groupe comprenant :les homopolymères, les copolymères incluant les terpolymères comprenant un ou plusieurs monomères d'acrylamide (AM), d'acide acrylique (AA), d'acide 2-acrylamide-méthyl-propane-sulfonique (AMPSA), d'acide méthacrylique (MAA), de méthacrylate éthoxylé, d'acide itaconique (IA), de polyéther-esters d'acide acrylique et d'acide méthacrylique et de polyéthers à base d'oxyde de polyéthylène et d'oxyde de polypropylène et leurs mélanges, comprenant le monométhacrylate de polyéthylène-glycol (PGM), l'anhydride maléique (MA), l'acide maléique (MA), le t-butyl-acrylamide (TBAM), le styrène-sulfonate de sodium (SSS), le vinyl-sulfonate de sodium, l'acrylate d'hydroxypropyle, le méthacrylate d'hydroxy-propyle, l'acide 3-allyloxy-2-hydroxy-propane-sulfonique (AHPS), et l'acide vinyl-phosphonique, dans lequel le poids moléculaire moyen en poids pour ces additifs polymères se situe dans la gamme d'environ 500 à 250 000.
- Une composition selon la revendication 11, dans laquelle l'additif polymère est choisi parmi le groupe comprenant l'acide polyacrylique et les copolymères 75/25 et 60/40 AA/AMPSA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/PGM-5 (ayant 5 motifs oxyéthylène se répétant), et AA/AMPSA/TBAM.
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US6083403A (en) * | 1998-11-05 | 2000-07-04 | Nalco Chemical Company | Stabilized substituted aminomethane-1, 1-diphosphonic acid n-oxides and use thereof in preventing scale and corrosion |
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US3434969A (en) * | 1967-08-11 | 1969-03-25 | Calgon Corp | Scale inhibiting |
US3518204A (en) * | 1967-11-01 | 1970-06-30 | Betz Laboratories | Control of the rate of precipitate growth and of precipitation in aqueous systems |
US4080375A (en) * | 1971-02-05 | 1978-03-21 | Petrolite Corporation | Methylene phosphonates of amino-terminated oxyalkylates and uses therefor |
US3928196A (en) * | 1973-12-05 | 1975-12-23 | Calgon Corp | Inhibition of scale deposition |
US3965027A (en) * | 1974-03-11 | 1976-06-22 | Calgon Corporation | Scale inhibition and corrosion inhibition |
US4088574A (en) * | 1974-03-27 | 1978-05-09 | Petrolite Corporation | Employing methylene phosphonates of oxyalkylated polyalkylene polyamines in chelation and/or scale inhibition |
US4457847B2 (en) * | 1981-11-05 | 1996-12-31 | Nalco Chemical Co | Carboxylate polymers for internal scale control agents in boiler systems |
US4936987A (en) * | 1983-03-07 | 1990-06-26 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
US4640793A (en) * | 1984-02-14 | 1987-02-03 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
US4671888A (en) * | 1984-12-03 | 1987-06-09 | Calgon Corporation | Polyelectrolyte and surfactant compositions for controlling alkaline earth metal scales |
US4650591A (en) * | 1985-08-29 | 1987-03-17 | Calgon Corporation | Acrylic acid/2-acrylamido-2-methylpropylsulfonic acid/2-acrylamido-2-methylpropyl phosphonic acid polymers as scale and corrosion inhibitors |
US4950474A (en) * | 1988-08-01 | 1990-08-21 | Texaco Inc. | Combination corrosion and scale inhibiting system containing phosphonate/amine reaction product |
US4931189A (en) * | 1988-11-02 | 1990-06-05 | Petrolite Corporation | Methods for inhibition of scale in high brine environments |
US5069798A (en) * | 1989-12-15 | 1991-12-03 | W. R. Grace & Co.-Conn. | Control of scale in aqueous systems using certain phosphonomethyl amines |
US4973744A (en) * | 1989-12-15 | 1990-11-27 | W. R. Grace & Co.-Conn. | Ethoxylated N,N-bis-phosphonomethyl 2-(hydroxy)ethylamine N-oxides and water-soluble salts thereof |
DE69217580T2 (de) * | 1991-05-31 | 1997-06-26 | Calgon Corp | Polyether-Polyamino-Methylenphosphonaten zur Kontrolle von Ablagerungen bei hohem pH-Wert |
US5322636A (en) * | 1992-03-30 | 1994-06-21 | Calgon Corporation | Polyether polyamino methylene phosphonate n-oxides for high pH scale control |
CA2092492A1 (fr) * | 1992-03-30 | 1993-10-01 | Ecc Specialty Chemicals Inc. | N-(2-hydroxyethyl)-n-bis (acide methylenephosphonique) et son n-oxyde correspondant utilise pour reduire l'entartrage a ph eleve |
-
1992
- 1992-03-30 US US07/860,373 patent/US5259974A/en not_active Expired - Lifetime
-
1993
- 1993-03-25 CA CA002092493A patent/CA2092493C/fr not_active Expired - Fee Related
- 1993-03-29 MX MX9301755A patent/MX9301755A/es unknown
- 1993-03-29 AU AU35583/93A patent/AU662212B2/en not_active Ceased
- 1993-03-29 JP JP5093615A patent/JPH0649081A/ja active Pending
- 1993-03-30 DE DE69328801T patent/DE69328801T2/de not_active Expired - Fee Related
- 1993-03-30 EP EP93302469A patent/EP0564232B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0649081A (ja) | 1994-02-22 |
AU3558393A (en) | 1993-10-07 |
CA2092493A1 (fr) | 1993-10-01 |
MX9301755A (es) | 1994-08-31 |
DE69328801D1 (de) | 2000-07-13 |
AU662212B2 (en) | 1995-08-24 |
DE69328801T2 (de) | 2001-02-22 |
US5259974A (en) | 1993-11-09 |
CA2092493C (fr) | 2006-12-19 |
EP0564232A1 (fr) | 1993-10-06 |
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